Direct calculation of solid-vapor coexistence points by thermodynamic integration: application to single component...

Area of Science:

• Physical Chemistry
• Computational Materials Science
• Chemical Thermodynamics

Background:

• Calculating phase transition temperatures, such as sublimation, is crucial for predicting material behavior.
• Traditional methods can be computationally intensive or require complex theoretical frameworks.

Purpose of the Study:

• To develop a novel thermodynamic integration method for direct calculation of sublimation temperatures.
• To extend the method for calculating binary mixture sublimation temperatures.

Main Methods:

• Utilizing thermodynamic integration in the isothermal-isobaric ensemble to directly link vapor and solid phases.
• Applying the isothermal-isobaric semigrand ensemble for binary mixtures without altering the integration path.

Main Results:

• The method accurately determines Gibbs free energy differences, enabling straightforward sublimation temperature calculation.
• Successfully extended to binary mixtures, yielding chemical potential differences for component sublimation.
• Predicted coexistence temperatures show excellent agreement with literature values for Lennard-Jones systems.

Conclusions:

• The presented thermodynamic integration method offers an efficient and accurate approach for determining sublimation temperatures.
• The method's adaptability to binary mixtures simplifies phase equilibrium studies in complex systems.